TWI672329B - Method of preparing a birefringent polymer film - Google Patents

Abstract

This invention relates to a method of making a polymer film and to the use of the polymer film as an alignment layer or optical retardation film in a liquid crystal display (LCD) or other optical or electro-optic device for decorative or security applications.

Description

Method for preparing birefringent polymer film

The present invention relates to a method of preparing a polymer film, the film itself, and the polymer film as an alignment layer in a liquid crystal display (LCD) or other optical or electro-optical device for decorative or security applications, for window applications Or the use of an optical retardation film.

Typically, the reactive liquid crystal original layer requires an alignment layer or a rubbed plastic substrate to align in a planar state. In this regard, two main methods are currently used in the display industry to align liquid crystals for optical film applications:

(i) A rubbing process in which a plastic substrate or alignment layer is rubbed in one direction for providing an alignment direction of the coated liquid crystal. The alignment quality varies depending on the friction process and the nature of the substrate or film. The rubbing process is difficult to optimize and can produce a variety of results. In addition, LCD manufacturers regard the rubbing process as an unsuitable process because the rubbing process can produce particles that are difficult to control in an advanced clean room.

(ii) A photoalignment process as described in US 7,364,671 B2, wherein the photo-directable monomer, oligomer or polymer is optically oriented while maintaining substantially inhibiting polymerization or cross-linking conditions of the polymerizable liquid crystal material. . The light alignment and polymerization steps are performed in two different steps and under different conditions. Therefore, it may be difficult to prepare such a light alignment layer due to the requirement that the production conditions have to be adjusted with respect to the individual compositions of various liquid crystal materials. Additionally, an annealing step is typically required to allow the liquid crystals to be perfectly aligned. Therefore, the light alignment layer obtained in accordance with this process is expensive.

Thus, there remains a need for alternative production methods that do not have the disadvantages of prior art methods or have such disadvantages as to a lesser extent.

It is an object of the present invention to provide a process for producing a polymer film which is particularly suitable for mass production; and b) suitable for a wide range of polymerizable liquid crystal materials; c) does not require, for example, tribological polymerization Alignment layer of amine layer; d) allow patterning; e) allow coating of selected layers without the need for additional alignment layers; f) allow for thick films with uneven alignment; and g) allow for flattening Type polymer concave lens or convex lens.

Other objects of the present invention will be immediately apparent to those skilled in the art from the following embodiments.

Unexpectedly, the inventors have discovered that one or more of the above problems can be solved by a method of making a polymeric film in accordance with the present invention, the method comprising the steps of: a) providing a layer of a polymerizable liquid crystal material onto a substrate, The polymerizable liquid crystal material comprises at least one dichroic photoinitiator and at least one pair of palmitic compounds; b) adjusting the temperature of the polymerizable liquid crystal material to a temperature in which the polymerizable liquid crystal material is in its nematic or isotropic phase; c) polymerizing and orienting by irradiating the polymerizable liquid crystal material with linearly polarized actinic radiation, thereby changing the angle between the polymerizable liquid crystal material layer and the direction of the electric field vector of the linearly polarized actinic radiation, thereby making the polymerizable The liquid crystal material forms a polymer film; and d) the polymer film is removed from the substrate as appropriate.

Advantageously, the method according to the invention eliminates the need for an alignment layer or a rubbing process. Can be used on many different substrates without further processing of the polymerizable liquid crystal material For example, a polymer film is produced on a flat glass, a color filter, or a plastic substrate. Curing can be performed in the isotropic phase of the polymerizable liquid crystal material or even in the nematic phase. Typical temperature ranges are from about 150 ° C below the respective clarification point to about 75 ° C above the corresponding clarification point, preferably from about 100 ° C below the corresponding clarification point to about 60 ° C above the corresponding clarification point, More preferably in the range of from about 75 ° C below the corresponding clarification point to about 50 ° C above the corresponding clarification point, but in all cases, the condition is that the liquid crystal material is in its nematic phase or in its isotropic phase. . It is desirable to combine a palm compound and a polarization sensitive photoinitiator with linearly polarized actinic radiation to induce, for example, planar or oblique alignment in the resulting optical film. The process of fabricating the polymer film can be accomplished in one step by linearly polarizing actinic radiation to produce, for example, a uniquely patterned polymer film that exhibits at least two different orientations of the liquid crystal director.

The invention further relates to polymeric films obtainable by the processes as described above and below.

The invention further relates to the use of a polymeric film as described above and below for use as an alignment layer or optical retardation in decorative or security applications, liquid crystal displays (LCDs) for window applications or other optical or electro-optic devices membrane.

Such optical and electro-optic devices include, but are not limited to, electro-optic displays, liquid crystal displays (LCDs), polarizers, compensators, beam splitters, reflective films, alignment films, 3D films (such as lens arrays, lenses), color Filters, holograms, hot stamping foils, color images, decorative or security markings, liquid crystal pigments, adhesive layers, nonlinear optical (NLO) devices, and optical information storage devices.

The invention further relates to a compensator comprising at least one polymeric film as described above and below, in particular a patterned A and C plate compensator and a tilted variant of the compensator.

The invention further relates to optical or electro-optical devices comprising at least one polymeric film as described above and below.

Terms and definitions

As used herein, the term "polymer" is understood to mean a molecule that encompasses the backbone of one or more different types of repeating units (the smallest constituent unit of a molecule) and includes the general terms "oligomer", "copolymer". "Homopolymer" and its analogues. In addition, it will be understood that, in addition to the polymer itself, the term polymer includes residues from the initiator, catalyst, and other elements accompanying the synthesis of the polymer, wherein the residues are understood to be uncombined. polymer. In addition, when normally removed during the post-polymerization purification process, the residues and other elements are typically mixed or blended with the polymer such that when the polymer is transferred between the containers or between the solvent or dispersion medium These residues and other elements are generally retained with the polymer.

The term "polymerization" means a chemical process for forming a polymer by joining together a plurality of polymerizable groups or polymer precursors (polymerizable compounds) containing the polymerizable groups.

The terms "film" and "layer" include rigid or flexible, self-supporting or freestanding films having mechanical stability and coatings or layers on or between a support substrate.

The term "liquid crystal (LC)" relates to a material having a liquid crystal intermediate phase in some temperature ranges (to a thermal LC) or in a concentration range (to a liquid LC) in a solution. These materials must contain liquid crystal precursor compounds.

The terms "liquid crystal original compound" and "liquid crystal compound" mean a compound containing one or more rod-like (rod-shaped or plate-shaped/stripe-shaped) or disc-shaped (disc-shaped) liquid crystal original groups. The term "liquid crystal original group" means a group capable of inducing the behavior of a liquid crystal phase (or an intermediate phase).

The compound containing a liquid crystal original group does not necessarily have to exhibit a liquid crystal intermediate phase. It is also possible for such compounds to exhibit a liquid crystal mesophase only in a mixture with other compounds or when a liquid crystal original compound or material or a mixture thereof is polymerized. This case includes a low molecular weight non-reactive liquid crystal compound, a reactive or polymerizable liquid crystal compound, and a liquid crystal polymer.

The rod-like liquid crystal original group usually comprises one or more groups directly or via a bonding group a liquid crystal core comprising a linked aromatic or non-aromatic cyclic group, optionally comprising an end group attached to the end of the liquid crystal core and optionally including one or more long sides attached to the original core of the liquid crystal The pendant groups, wherein the terminal groups and pendant groups are typically selected from, for example, a carbyl or hydrocarbyl group, a polar group (e.g., a halogen, a nitro group, a hydroxyl group, etc.) or a polymerizable group.

The term "reactive mesogen" means a polymerizable liquid crystal original compound or a liquid crystal compound, preferably a monomer compound. These compounds can be used as pure compounds or as mixtures of reactive liquid crystals with other compounds which act as photoinitiators, inhibitors, surfactants, stabilizers, chain transfer agents, non-polymerizable compounds and the like.

A polymerizable compound having one polymerizable group is also referred to as a "single-reactive" compound, and a compound having two polymerizable groups is referred to as a "dual-reactive" compound, and has two or more polymerizable groups. Compounds are referred to as "multi-reactive" compounds. A compound having no polymerizable group is also referred to as a "non-reactive or non-polymerizable" compound.

The term "pair of palms" is generally used to describe objects that cannot be superimposed on their mirrors. A "non-palphasity" (non-palphasity) object is the same object as its mirror.

The first approximation by the ratio of the palmar substance (P ₀ ) is inversely proportional to the concentration (c) of the palm material used. The proportionality constant of this relationship is called the helical torsion force (HTP) of the palm material and is defined by equation (1) HTP=1/(c.P ₀ ) (1)

Where (c) is the concentration of the palm compound.

As with common photoinitiators, the "dichroic photoinitiator" dissociates when exposed to the correct wavelength. In fact, at least two free radicals are formed, at least one of which is capable of initiating polymerization of the monomers. Dichroic photoinitiators have the property that light absorption is dependent on the molecular orientation of the molecule. The dichroic photoinitiator selectively dissociates when aligned with the electric field vector of the incident light.

Linearly polarized light is understood to mean that the electric field vector or magnetic field vector is limited to light in the form of a transverse wave in a given plane along the direction of propagation. Defining a linear pole by the direction of the electric field vector Orientation of the light. For example, when the electric field vector is vertical (alternating up and down as the wave travels), the radiation is said to be vertically polarized.

Visible light is electromagnetic radiation having a wavelength in the range of from about 400 nm to about 740 nm. Ultraviolet (UV) light is electromagnetic radiation having a wavelength in the range of from about 200 nm to about 450 nm.

The irradiance (E _e ) or the radiant power is defined as the power of electromagnetic radiation (dθ) per unit area (dA) incident on the surface: E _e = dθ / dA. (2)

The radiation exposure or radiation dose (H _e ) is defined as the irradiance or radiant power (E _e ) per time (t): H _e = E _e . t. (3)

All temperatures of the liquid crystal, such as melting point T (C, N) or T (C, S), from smectic (S) to nematic (N) phase T (S, N) and clarification point T (N, I) They are all quoted in degrees Celsius. All temperature differences are quoted as differences. The term "clarification point" means the temperature at which a transition between an intermediate phase and an isotropic phase having the highest temperature range occurs.

The term "director" is known in the prior art and means a preferred orientation of the long molecular axis of the liquid crystal or RM molecule (in the case of a rod-like compound) or the short molecular axis (in the case of a disc-shaped compound). . If the anisotropic molecules are uniaxially ordered, the director is an anisotropic axis.

The term "alignment" or "orientation" refers to the alignment (orientation ordering) of an anisotropic unit of a material, such as a segment of a small molecule or a macromolecule, in a common direction known as the "alignment direction." In the alignment layer of the liquid crystal or RM material, the liquid crystal directors are aligned with the alignment direction such that the alignment direction corresponds to the direction of the anisotropic axis of the material.

The term "uniform orientation" or "uniform alignment" of a liquid crystal or RM material (eg, in the layer of the material) means the long molecular axis of the liquid crystal or RM molecule (in the case of a rod compound) or the short molecular axis ( In the case of a disc shaped compound) it is oriented substantially in the same direction. change In other words, the lines of the liquid crystal guide are parallel.

The term "planar orientation/alignment" (eg, in the layer of liquid crystal or RM material) means the long molecular axis of a liquid crystal or RM molecule (in the case of a rod-like compound) or a short molecular axis (in the form of a disc-shaped compound) In this case) oriented substantially parallel to the plane of the layer.

The term "inclined orientation/alignment" (eg, in the layer of liquid crystal or RM material) means the long molecular axis of a liquid crystal or RM molecule (in the case of a rod-like compound) or a short molecular axis (in the form of a disc-shaped compound) In this case, the plane is oriented at an angle θ ("inclination angle") between 0° and 90° with respect to the plane of the layer.

The birefringence Δn is defined as follows n=n _e -n _o (4)

Where n _e is an abnormal refractive index and n _o is a normal refractive index, and an average refractive index n _av. is given by the following equation: n _av. = ((2n _o ² + n _e ² )/3) ^1⁄2 ( 5)

The Abbe's refractive index can be used to measure the average refractive index n _av. and the normal refractive index n _o . Δn can then be calculated from the above equation.

If in doubt, the definitions given in C. Tschierske, G. Pelzl and S. Diele, Angew. Chem. 2004, 116, 6340-6368 should be applied.

1‧‧‧Light source

2‧‧‧Linear polarizer

3‧‧‧Photomask

4‧‧‧Substrate

5‧‧‧heat source

6‧‧‧Rotary table

7‧‧‧Light source

8‧‧‧ Beam

9‧‧‧Linear polarizer

10‧‧‧Photomask

11‧‧‧Substrate

12‧‧‧heat source

13‧‧‧Rotary table

Figure 1 shows the configuration of a production method according to the present invention.

Figure 2 shows the orientation of the wire grid polarizer relative to the slit mask for radially aligning the polymer film.

Figure 3 shows a clear transparent polymer film with good radial orientation.

Figure 4 shows the orientation of the wire grid polarizer relative to the slit mask for concentric alignment of the polymer film.

Figure 5 shows a clear transparent polymer film with a good concentric orientation.

Figure 6 shows the configuration of a production method according to the present invention.

Figure 7 shows a clear transparent polymer film with a good orientation in a convexly oriented form.

Figure 8 shows the configuration of a production method according to the present invention.

In a preferred embodiment, the polymerizable liquid crystal material used in the method according to the invention comprises at least one monoreactive, dual reactive or polyreactive polymerizable liquid crystal precursor compound, at least one antagonistic compound and at least one A color photoinitiator.

In another preferred embodiment, the polymerizable liquid crystal material used in the method according to the present invention comprises at least one monoreactive polymerizable liquid crystal precursor compound, at least one double reactive or polyreactive polymerizable liquid crystal precursor compound, at least one A palmitic compound and at least one dichroic photoinitiator.

In other preferred embodiments, the polymerizable liquid crystal material used in the method according to the present invention comprises at least one monoreactive pair of palm polymerizable liquid crystal precursor compounds, at least one single reactivity, double reactivity or multiple reactivity non-pair A palmitic polymerizable liquid crystal precursor compound and at least one dichroic photoinitiator.

In particular, the polymerizable liquid crystal material used in the method according to the invention comprises at least one double reactive or polyreactive pair of palmitic polymerizable liquid crystal precursor compounds, at least one single reactive, double reactive or multiple reactive non-pair A palmitic polymerizable liquid crystal precursor compound and at least one dichroic photoinitiator.

Also preferably, the polymerizable liquid crystal material comprises at least one non-polymerizable palmitic compound, at least one monoreactive, double reactive or polyreactive non-pivotic polymerizable liquid crystal precursor compound and at least one dichroic photoinitiator .

All known dichroic photoinitiators are suitable for the process according to the invention, preferably using a dichroic photoinitiator comprising an alpha-amine group as disclosed in EP 1 388 538 A1. Particularly preferred is a dichroic photoinitiator of formula I,

Wherein P is a polymerizable group; Sp is a spacer group or a single bond; and A ^{11 is} independently, independently of each other, an aryl group or a heteroaryl group optionally substituted with one or more identical or different groups L. a group, an aliphatic group or a heterocyclic group; Z ¹¹ is independently of each other -O-, -S-, -CO-, -COO-, -OCO-, -S-CO-, -CO- S-, -O-COO-, -CO-NR ⁰¹ -, -NR ⁰¹ -CO-, -NR ⁰¹ -CO-NR ⁰² , -NR ⁰¹ -CO-O-, -O-CO-NR ⁰¹ -, -OCH ₂ -, -CH ₂ O-, -SCH ₂ -, -CH ₂ S-, -CF ₂ O-, -OCF ₂ -, -CF ₂ S-, -SCF ₂ -, -CH ₂ CH ₂ - , -(CH ₂ ) ₄ -, -CF ₂ CH ₂ -, -CH ₂ CF ₂ -, -CF ₂ CF ₂ -, -CH=N-, -N=CH-, -N=N-, -CH =CR ⁰¹ -, -CY ⁰¹ =CY ⁰² -, -C≡C-, -CH=CH-COO-, -OCO-CH=CH- or single bond; m is 0, 1, 2 or 3; r is 0, 1, 2, 3 or 4; L in the case of multiple occurrences independently of each other H, halogen, CN or, as the case may be mono- or polysubstituted by halogen or CN, a linear chain of 1 to 5 C atoms or branched alkyl group, and wherein one or more non-adjacent CH ₂ groups such that O and / or S atoms are not bonded directly to one another independently of, as appropriate in each case to one another By -O -, - S -, - NR 01 -, - SiR 01 R 02 -, - CO -, - COO -, - OCO -, - OCO-O -, - NR 01 -CO -, - CO-NR ⁰¹ -, -NR ⁰¹ -CO-NR ⁰² -, -S-CO-, -CO-S-, -CY ⁰¹ =CY ⁰² - or -C≡C-substitution; R ¹¹ is H, halogen, CN, NO ₂ , NCS, SF ₅ , P-Sp-; or a linear or branched alkyl group having 1 to 20 C atoms, which may be mono- or polysubstituted by halogen or CN, and one or more of which are non-adjacent The CH ₂ groups are independently selected from each other by -O-, -S-, -NR ⁰¹ -, -SiR ⁰¹ R ⁰² -, - in such a manner that the O and/or S atoms are not directly bonded to each other. CO-, -COO-, -OCO-, -OCO-O-, -NR ⁰¹ -CO-, -CO-NR ⁰¹ -, -NR ⁰¹ -CO-NR ⁰² -, -S-CO-, -CO- S-, -CY ⁰¹ =CY ⁰² - or -C≡C-substitution; or R ¹⁴ ; R ^12-13 independently of each other H or, as the case may be mono- or polysubstituted by halogen or CN, having 1 to 5 C a linear or branched alkyl group of an atom, and wherein one or more non-adjacent CH ₂ groups are independently taken from each other independently in each case in such a manner that the O and/or S atoms are not directly bonded to each other. -, -S-, -NR ⁰¹ -, -SiR ⁰¹ R ⁰² -, -CO-, -COO-, -OCO-, -OCO-O-, - NR ⁰¹ -CO-, -CO-NR ⁰¹ -, -NR ⁰¹ -CO-NR ⁰² -, -S-CO-, -CO-S-, -CY ⁰¹ =CY ⁰² - or -C≡C-substitution; R ¹⁴ represents -OH, -NR ⁰¹ R ⁰² or Y ⁰¹ and Y ⁰² each independently represent H, halogen or CN; and R ⁰¹ and R ⁰² are each independently H or a linear or branched alkyl group having 1 to 5 C atoms.

Above and below, "carbon-based" means a monovalent or polyvalent organic group containing at least one carbon atom which does not contain other atoms (such as, for example, -C≡C-) or optionally contains one or A plurality of other atoms such as, for example, N, O, S, P, Si, Se, As, Te or Ge (e.g., carbonyl, etc.). "Hydrocarbyl" means a carbon radical which additionally contains one or more H atoms and optionally one or more heteroatoms such as, for example, N, O, S, P, Si, Se, As, Te or Ge.

"Halogen" means F, Cl, Br or I, preferably F.

The carbyl or hydrocarbyl group can be a saturated or unsaturated group. The unsaturated group is, for example, an aryl group, an alkenyl group or an alkynyl group. a carbon group or a hydrocarbon group having 3 or more C atoms may be a linear chain branch And/or cyclic and may contain a spiro bond or a condensed ring.

Above and below, the terms "alkyl", "aryl", "heteroaryl" and the like also encompass polyvalent groups (eg, alkyl, aryl, heteroaryl, etc.). The term "aryl" means an aromatic carbon group or a group derived from the aromatic carbon group. The term "heteroaryl" means an "aryl" group as defined above containing one or more heteroatoms.

Preferred carbon and hydrocarbyl groups are optionally substituted alkyl, alkenyl, alkynyl, alkoxy, alkylcarbonyl, alkane having from 1 to 40, preferably from 1 to 25, particularly preferably from 1 to 18, C atoms. An oxycarbonyl group, an alkylcarbonyloxy group and an alkoxycarbonyloxy group, optionally having an substituted aryl or aryloxy group of 6 to 40, preferably 6 to 25 C atoms, or having 6 to 40, preferably 6 Substituting alkyl aryl, arylalkyl, alkyl aryloxy, arylalkoxy, arylcarbonyl, aryloxycarbonyl, arylcarbonyloxy and aryloxy to 25 C atoms Carbonyloxy.

Other preferred carbyl and hydrocarbyl group of: C ₁ -C ₄₀ alkyl, C ₂ -C ₄₀ alkenyl, C ₂ -C ₄₀ alkynyl, C ₃ -C ₄₀ allyl group, C ₄ -C ₄₀ alkyl di Alkenyl, C ₄ -C ₄₀ polyalkenyl, C ₆ -C ₄₀ aryl, C ₆ -C ₄₀ alkylaryl, C ₆ -C ₄₀ arylalkyl, C ₆ -C ₄₀ alkylaryloxy And a C ₆ -C ₄₀ arylalkoxy group, a C ₂ -C ₄₀ heteroaryl group, a C ₄ -C ₄₀ cycloalkyl group, a C ₄ -C ₄₀ cycloalkenyl group or the like. Particularly preferred is a C ₁ -C ₂₂ alkyl, C ₂ -C ₂₂ alkylene group, C ₂ -C ₂₂ an alkynyl group, C ₃ -C ₂₂ allyl group, C ₄ -C ₂₂ alkyldienyl, C ₆ -C ₁₂ aryl, C ₆ -C ₂₀ aralkyl and C ₂ -C ₂₀ heteroaryl.

Other preferred carbyl and hydrocarbyl groups are unsubstituted or monosubstituted or polysubstituted by F, Cl, Br, I or CN having from 1 to 40, preferably from 1 to 25, C, more preferably from 1 to 12, C atoms. a straight chain, a branched chain or a cyclic alkyl group, and wherein one or more non-adjacent CH ₂ groups may be such that the O and/or S atoms are not directly bonded to each other, respectively, independently of each other by -C (R ^x )=C(R ^x )-, -C≡C-, -N(R ^x )-, -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O- replacement.

R ^x preferably denotes H, a halogen, a linear, branched or cyclic alkyl chain having 1 to 25 C atoms, wherein, in addition, one or more non-adjacent C atoms may pass through -O-, -S -, -CO-, -CO-O-, -O-CO-, -O-CO-O- and wherein one or more H atoms may be substituted by fluorine, optionally with 6 to 40 C atoms The aryl or aryloxy group, or optionally substituted heteroaryl or heteroaryloxy group having 2 to 40 C atoms, is substituted.

Preferred alkyl groups are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-butyl, 2-methylbutyl, n-pentyl, Dipentyl, cyclopentyl, n-hexyl, cyclohexyl, 2-ethylhexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, n-decyl, n-decyl, n-undecyl, N-dodecyl, dodecyl, trifluoromethyl, perfluoro-n-butyl, 2,2,2-trifluoroethyl, perfluorooctyl, perfluorohexyl, and the like.

Preferred alkenyl groups are, for example, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctene Base.

Preferred alkynyl groups are, for example, ethynyl, propynyl, butynyl, pentynyl, hexynyl, octynyl and the like.

Preferred alkoxy groups are, for example, methoxy, ethoxy, 2-methoxyethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, second butoxy, Third butoxy, 2-methylbutoxy, n-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, n-decyloxy, n-decyloxy, n-undecyloxy, N-dodecyloxy and the like.

Preferred amine groups are, for example, dimethylamino, methylamino, methylphenylamino, phenylamino and the like.

The aryl and heteroaryl groups may be monocyclic or polycyclic, that is, they may have one ring (such as, for example, a phenyl group) or two or more rings (such as, for example, a naphthyl group) which may also be fused. Either covalently linked (such as, for example, biphenyl) or a combination of a fused ring and a bonded ring. The heteroaryl group contains one or more heteroatoms preferably selected from the group consisting of O, N, S and Se.

Particularly preferred are monocyclic, bicyclic or tricyclic aryl groups having 6 to 25 C atoms and monocyclic, bicyclic or tricyclic heteroaryl groups having 2 to 25 C atoms, which optionally contain a fused ring and The situation was replaced. Further, it is preferably a 5-, 6- or 7-membered aryl group and a heteroaryl group, wherein, in addition, one or more CH groups may be such that N atoms and/or S atoms are not directly bonded to each other by N, S or O replacement.

Preferred aryl groups are, for example, phenyl, biphenyl, triphenyl, [1,1':3',1"]biphenyl-2'-yl, naphthyl, anthracene, binaphthyl, phenanthrene, anthracene, di Hydroquinone, , hydrazine, tetracene, pentacene, benzopyrene, hydrazine, hydrazine, hydrazine, hydrazine, etc.

Preferred heteroaryl groups are, for example, 5-membered rings (such as pyrrole, pyrazole, imidazole, 1,2,3-triazole, 1,2,4-triazole, tetrazole, furan, thiophene, selenophene, oxazole). , isoxazole, 1,2-thiazole, 1,3-thiazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3 , 4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole), 6 members Ring (such as pyridine, pyridazine, pyrimidine, pyrazine, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, 1,2,4,5-tetra Pyrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine) or a condensed group (such as hydrazine, isoindole, pyridazine, oxazole, benzimidazole, benzo) Triazole, anthracene, naphthimidazole, phenamimidazole, pyridoimidazole, pyrazinoimidazole, quinoxalinimidazole, benzoxazole, naphthoazole, oxazole, phenazole, isoxazole, benzene Thiazole, benzofuran, isobenzofuran, dibenzofuran, quinoline, isoquinoline, acridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo- 7,8-quinoline, benzoisoquinoline, acridine, phenothiazine, phenoxazine, benzoxazine, benzopyrimidine, quinololine, phenazine, naphthyridine, anthracene , benzoporphyrin, phenanthridine, phenanthroline, thieno[2,3b]thiophene, thieno[3,2b]thiophene, dithienothiophene, isobenzothiophene, dibenzothiophene, benzothiadiazole And thiophene) or a combination of such groups. Heteroaryl groups can also be substituted with alkyl, alkoxy, sulfanyl, fluoro, fluoroalkyl or other aryl or heteroaryl groups.

(Non-aromatic) alicyclic and heterocyclic groups encompass both saturated rings (ie, monocyclic rings containing a single bond) and partially unsaturated rings (ie, may also contain a ring of complex bonds) . The heterocycle contains one or more heteroatoms preferably selected from the group consisting of Si, O, N, S and Se.

The (non-aromatic) alicyclic and heterocyclic groups may be monocyclic, that is, contain only one ring (such as, for example, cyclohexane), or multiple rings, that is, contain a plurality of rings (such as, for example, decahydro) Naphthalene or bicyclooctane). Particularly preferred is a saturated group. Further, a monocyclic, bicyclic or tricyclic group having 3 to 25 C atoms, which optionally contains a fused ring and optionally is substituted, is preferred. Further, a 5, 6, 7 or 8 membered carbocyclic group is preferred, wherein, in addition, one or more C atoms may be replaced by Si and/or one or more CH groups may be replaced by N and/or one or A plurality of non-adjacent CH ₂ groups may be replaced by -O- and/or -S-.

Preferred alicyclic and heterocyclic groups are, for example, a 5-member group (such as cyclopentane, tetrahydrofuran, tetrahydrothiofuran, pyrrolidine), a 6-member group (such as cyclohexane, cyclohexane). ), cyclohexene, tetrahydropyran, tetrahydrothiopyran, 1,3-dioxane, 1,3-dithiane, piperidine), a 7-member group (such as cycloheptane), and fused a group (such as tetralin, decalin, indane, bicyclo[1.1.1]-pentane-1,3-diyl, bicyclo[2.2.2]octane-1,4-diyl, spiro [3.3] Heptane-2,6-diyl, octahydro-4,7-methyleneindan-2,5-diyl).

The aryl, heteroaryl, carbyl and hydrocarbyl groups optionally have one or more substituents, preferably selected from the group consisting of decyl, sulfonate, sulfonyl, decyl, amine , imine, nitrile, mercapto, nitro, halogen, C _1-12 alkyl, C _6-12 aryl, C _1-12 alkoxy, hydroxy or a combination of such groups.

Preferred substituents are, for example, a group which promotes dissolution (such as an alkyl group or an alkoxy group), an electron withdrawing group such as fluorine, a nitro group or a nitrile, or a substitution for increasing the glass transition temperature (Tg) of the polymer. A radical, especially a bulky group, such as a tributyl or an optionally substituted aryl.

Preferred substituents (hereinafter also referred to as "L") are, for example, F, Cl, Br, I, OH, -CN, -NO ₂ , -NCO, -NCS, -OCN, -SCN, -C(=O) N(R ^x ) ₂ , -C(=O)Y ¹ , -C(=O)R ^x , -C(=O)OR ^x , -N(R ^x ) ₂ , wherein R ^x has the above mentioned And Y ¹ represents halogen, optionally substituted anthracenyl, optionally substituted aryl or heteroaryl having 4 to 40, preferably 4 to 20 ring atoms and having 1 to 25 C atoms a straight or branched alkyl, alkenyl, alkynyl, alkoxy, alkylcarbo, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy group, wherein one or more H atoms may be used as appropriate Replaced by F or Cl.

"Substituted alkyl or aryl" preferably means via halogen, -CN, R ⁰ , -OR ⁰ , -CO-R ⁰ , -CO-OR ⁰ , -O-CO-R ⁰ or -O -CO-OR ⁰ substitution, wherein R ⁰ has the meanings mentioned above.

Particularly preferred substituents L are, for example, F, Cl, CN, NO ₂ , CH ₃ , C ₂ H ₅ , OCH ₃ , OC ₂ H ₅ , COCH ₃ , COC ₂ H ₅ , COOCH ₃ , COOC ₂ H ₅ , CF ₃ , OCF ₃ , OCHF ₂ , OC ₂ F ₅ , in addition to phenyl.

Substituted phenyl ring in the formula shown above and below Preferred , , , or ; wherein, L, each of the same or different, has one of the meanings given above and below, and is preferably F, Cl, CN, NO ₂ , CH ₃ , C ₂ H ₅ , C (CH ₃ ) ₃ , CH(CH ₃ ) ₂ , CH ₂ CH(CH ₃ )C ₂ H ₅ , OCH ₃ , OC ₂ H ₅ , COCH ₃ , COC ₂ H ₅ , COOCH ₃ , COOC ₂ H ₅ , CF ₃ , OCF ₃ , OCHF ₂ , OC ₂ F ₅ or P-Sp-, excellently F, Cl, CN, CH ₃ , C ₂ H ₅ , OCH ₃ , COCH ₃ , OCF ₃ or P-Sp-, most Preferably, it is F, Cl, CH ₃ , OCH ₃ , COCH ₃ or OCF ₃ .

The polymerizable group P is preferably selected from the group consisting of a C=C double bond or a C≡C triple bond and a group suitable for ring opening polymerization such as, for example, propylene oxide or epoxy.

The polymerizable group P is preferably selected from the group consisting of CH ₂ =CW ¹ -COO-, CH ₂ =CW ¹ -CO-, , , , , CH ₂ =CW ² -(O) _k3 -, CW ¹ =CH-CO-(O) _k3 -, CW ¹ =CH-CO-NH-, CH ₂ =CW ¹ -CO-NH-,CH ₃ - CH=CH-O-, (CH ₂ =CH) ₂ CH-OCO-, (CH ₂ =CH-CH ₂ ) ₂ CH-OCO-, (CH ₂ =CH) ₂ CH-O-, (CH ₂ = CH-CH ₂ ) ₂ N-, (CH ₂ =CH-CH ₂ ) ₂ N-CO-, CH ₂ =CW ¹ -CO-NH-,CH ₂ =CH-(COO) _k1 -Phe-(O) _K2 -, CH ₂ =CH-(CO) _k1 -Phe-(O) _k2 -, Phe-CH=CH-, where W ¹ represents H, F, Cl, CN, CF ₃ , having 1 to 5 C atoms Phenyl or alkyl, especially denotes H, F, Cl or CH ₃ ; W ² represents H or an alkyl group having 1 to 5 C atoms, especially denotes H, methyl, ethyl or n-propyl; W ³ And W ⁴ each independently represent H, Cl or an alkyl group having 1 to 5 C atoms; Phe represents 1, as defined above, but different from P-Sp, substituted by one or more groups L, 4-phenylene; and k ₁ , k ₂ and k ₃ each independently represent 0 or 1; k ₃ preferably represents 1 and k ₄ is an integer from 1 to 10.

Particularly preferred groups P are CH ₂ =CH-COO-, CH ₂ =C(CH ₃ )-COO-, CH ₂ =CF-COO-, CH ₂ =CH-,CH ₂ =CH-O-, ( CH ₂ =CH) ₂ CH-OCO-, (CH ₂ =CH) ₂ CH-O-, and In particular, it is a vinyloxy group, an acrylate, a methacrylate, a fluoroacrylate, a chloroacrylate, a propylene oxide and an epoxide, and is preferably an acrylate or a methacrylate. In another preferred embodiment of the present invention, all polymerizable compounds and their subformulas contain one or more branched chain groups (containing two or more polymerizable groups P (polyreactive polymerizable groups) )) instead of one or more groups P-Sp-. Suitable groups of this type and polymerizable compounds containing such groups are described, for example, in US 7,060,200 B1 or US 2006/0172090 A1. Particularly preferred is a polyreactive polymerizable group selected from the group consisting of: -X-alkyl-CHP ¹ -CH ₂ -CH ₂ P ² I*a

-X-alkyl-C(CH ₂ P ¹ )(CH ₂ P ² )-CH ₂ P ³ I*b

-X-alkyl-CHP ¹ CHP ² -CH ₂ P ³ I*c

-X-alkyl-C(CH ₂ P ¹ )(CH ₂ P ² )-C _aa H _2aa+1 I*d

-X-alkyl-CHP ¹ -CH ₂ P ² I*e

-X-alkyl-CHP ¹ P ² I*f

-X-alkyl-CP ¹ P ² -C _aa H _2aa+1 I*g

-X-Alkyl-C(CH ₂ P ¹ )(CH ₂ P ² )-CH ₂ OCH ₂ -C(CH ₂ P ³ )(CH ₂ P ⁴ )CH ₂ P ⁵ I*h

-X-alkyl-CH((CH ₂ ) _aa P ¹ )((CH ₂ ) _bb P ² ) I*i

-X-alkyl-CHP ¹ CHP ² -C _aa H _2aa+1 I*k

Wherein: alkyl represents a single bond or a straight or branched alkyl group having 1 to 12 C atoms, wherein one or more non-adjacent CH ₂ groups may cause O and/or S atoms not to directly bond to each other The modes are each independently -C(R ^x )=C(R ^x )-, -C≡C-, -N(R ^x )-, -O-, -S-, -CO-, -CO -O-, -O-CO-, -O-CO-O-substitution, and wherein, in addition, one or more H atoms may be replaced by F, Cl or CN, wherein R ^x has the meanings mentioned above and Preferably, R ⁰ as defined above; aa and bb each independently represent 0, 1, 2, 3, 4, 5 or 6; X has one of the meanings indicated by X'; and P ^{1- 5} each independently of one another has one of the meanings indicated above with respect to P.

Preferably, the spacer group Sp is selected from the formulas Sp'-X' such that the group "P-Sp-" conforms to the formula "P-Sp'-X'-", wherein Sp' represents F, Cl, as appropriate. Br, I or CN mono- or polysubstituted alkylene having 1 to 20, preferably 1 to 12, C atoms, and wherein, in addition, one or more non-adjacent CH ₂ groups may cause O And/or the S atoms are not directly bonded to each other independently of each other by -O-, -S-, -NH-, -NR ⁰¹ -, -SiR ⁰¹ R ⁰² -, -CO-, -COO-, - OCO-, -OCO-O-, -S-CO-, -CO-S-, -NR ⁰¹ -CO-O-, -O-CO-NR ⁰¹ -, -NR ⁰¹ -CO-NR ⁰¹ -,- CH=CH- or -C≡C-substitution; X' represents -O-, -S-, -CO-, -COO-, -OCO-, -O-COO-, -CO-NR ⁰¹ -, -NR ⁰¹ -CO-, -NR ⁰¹ -CO-NR ⁰¹ -, -OCH ₂ -, -CH ₂ O-, -SCH ₂ -, -CH ₂ S-, -CF ₂ O-, -OCF ₂ -, -CF ₂ S-, -SCF ₂ -, -CF ₂ CH ₂ -, -CH ₂ CF ₂ -, -CF ₂ CF ₂ -, -CH=N-, -N=CH-, -N=N-, -CH =CR ⁰¹ -, -CY ⁰¹ =CY ⁰² -, -C≡C-, -CH=CH-COO-, -OCO-CH=CH- or a single bond; R ⁰¹ and R ⁰² each independently represent H or An alkyl group having 1 to 12 C atoms; and Y ⁰¹ and Y ⁰² each independently represent H, F, C l or CN.

X' is preferably -O-, -S-, -CO-, -COO-, -OCO-, -O-COO-, -CO-NR ⁰ -, -NR ⁰¹ -CO-, -NR ⁰¹ - CO-NR ⁰¹ - or single button.

A typical spacer group Sp' is, for example, -(CH ₂ ) _p1 -, -(CH ₂ CH ₂ O) _q1 -CH ₂ CH ₂ -, -CH ₂ CH ₂ -S-CH ₂ CH ₂ -, -CH ₂ CH ₂ -NH-CH ₂ CH ₂ - or -(SiR ⁰¹ R ⁰² -O) _p1 -, wherein p1 is an integer from 1 to 12, q1 is an integer from 1 to 3 and R ⁰¹ and R ⁰² have the above-mentioned definition.

Particularly preferred groups -X'-Sp'- are -(CH ₂ ) _p1 -, -O-(CH ₂ ) _p1 -, -OCO-(CH ₂ ) _p1 -, -OCOO-(CH ₂ ) _p1 - .

In each case, a particularly preferred group Sp' is, for example, a linear stretch ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, a decyl group, a decyl group, a hydrazine group. , undecyl, ten-decyl, octadecyl, ethyl ethoxy, ethyl methoxy, butyl, ethyl thio, ethyl, N-methyl The imino group extends an ethyl group, a 1-methylalkylene group, a vinyl group, a propylene group and a butenyl group.

Preferred dichroic photoinitiators useful in the process according to the invention are as follows

Wherein L, each occurrence and independently of each other, represents halogen, preferably F or Br; r each represents 0, 1 or 2 independently of each other; Z ¹¹ represents -O-, -S-, -CO-, -COO-, -OCO-, -S-CO-, -CO-S-, -O-COO-, -CO-NR ⁰¹ -, -NR ⁰¹ -CO-, -NR ⁰¹ -CO- NR ⁰² , -NR ⁰¹ -CO-O-, -O-CO-NR ⁰¹ -, -OCH ₂ -, -CH ₂ O-, -SCH ₂ -, -CH ₂ S-, -CF ₂ O-, - OCF ₂ -, -CF ₂ S-, -SCF ₂ -, -CH ₂ CH ₂ -, -(CH ₂ ) ₄ -, -CF ₂ CH ₂ -, -CH ₂ CF ₂ -, -CF ₂ CF ₂ - , -CH=N-, -N=CH-, -N=N-, -CH=CR ⁰¹ -, -CY ⁰¹ =CY ⁰² -, -C≡C-, -CH=CH-COO-, -OCO -CH=CH-; R ¹¹ represents a linear or branched alkyl group having 1 to 12 C atoms, which may be mono- or polysubstituted, as appropriate, and one or more non-adjacent CH ₂ groups thereof The manner in which the O and/or S atoms are not directly bonded to each other is, in each case, independently of -O-, -S-, as appropriate; P-Sp-; or R ¹⁴ ; R ^12-13 are independently of each other H or a linear alkyl group having 1 to 5 C atoms; R ¹⁴ represents -OH, -NR ⁰¹ R ⁰² or Y ⁰¹ and Y ⁰² each independently represent H, F, Cl or CN; and R ⁰¹ and R ⁰² are each independently H or a linear or branched alkyl group having 1 to 5 C atoms.

A particularly preferred dichroic photoinitiator is selected from the group consisting of

Wherein R ¹⁴ represents -OH, -NH ₂ or And R ¹¹ represents a linear or branched alkyl group having 1 to 12 C atoms, which may be mono- or polysubstituted, as appropriate, and wherein one or more non-adjacent CH ₂ groups are such that O and/or S atoms are not linked directly to one another independently of one another depending on the linkage of in each case substituted with -O -, - S- substituted; P-Sp-; or R ^14.

Particularly preferred dichroic photoinitiators are compounds of formulae I-2a and I-5a (wherein R ¹⁴ represents -OH), compounds of formula I-2a (wherein R ¹⁴ represents -NH ₂ ) and formulae I-2a to a compound of I-2e, I-3a to I-3d, I-4a to I-4b, I-6a, I-7a, I-7b and I-8a, wherein R ¹⁴ represents

The proportion of the dichroic photoinitiator in the preferred liquid crystal material for use in the process according to the invention is preferably in the range of from about 1% by weight to about 25% by weight, more preferably from about 3% by weight to about 20%. Within the range of % by weight and even more preferably in the range of from 5% by weight to about 15% by weight.

Suitable palmitic compounds in accordance with the present invention may be polymerizable or non-polymerizable.

The polymerizable chiral compound of the preferred use of the present invention individually or in combination with one another preferably of 25 m ^-1 or more, preferably of 40 m ^-1 or more, more preferably 60μm or more of the range of ^-1 The absolute value of the helical torsional force ( I HTP _total I ) in the range of 80 μm ^-1 or higher to 260 μm ^-1 or lower.

Preferably, the polymerizable palmitic compound can be a monoreactive, direactive or polyreactive palladium polymerizable liquid crystal precursor compound. Preferably, the compounds comprise one or more ring elements bonded to each other by a direct bond or via a linking group, and wherein two of the ring elements are optionally or directly via a bond The linking groups are bonded to each other, and the linking group may be the same as or different from the bonding group mentioned. Preferably, the ring elements are selected from the group of 4, 5, 6 or 7 membered rings, preferably a group of 5 or 6 membered rings.

Suitable polymerizable palmitic compounds and their synthesis are described, for example, in US 7,223,450 B2 or commercially available as Paliocolor LC756® (BASF AG).

Preferred mono-reactive, bi-reactive or poly-reactive palladium polymerizable liquid crystal precursor compounds for use in accordance with the present invention are selected from the group consisting of

Wherein P ⁰ is a polymerizable group independently of each other, preferably a propenyl group, a methacryl group, a propylene oxide, an epoxy group, a vinyl group, a vinyloxy group, a propenyl ether or a benzene group. Vinyl; A ⁰ and B ⁰ , independently of each other, are 1,4-phenylene, or trans-1,4-, substituted by 1, 2, 3 or 4 groups L, as appropriate. Extending cyclohexyl; X ⁰ and Z ⁰ independently of each other are -COO-, -OCO-, -CH ₂ CH ₂ -, -C≡C-, -CH=CH-, -CH= CH-COO-, -OCO-CH=CH- or a single bond; R* is a palmitic alkyl or alkoxy group having 4 or more, preferably 4 to 12, C atoms, such as 2- Methyl butyl, 2-methyloctyl, 2-methylbutoxy or 2-methyloctyloxy; Ch is a palmitic group selected from the group consisting of cholesterol, estradiol or anthraquinone groups, such as Menthol or citronella; L having one of the meanings as defined above in Formula I; r is 0, 1, 2, 3 or 4, preferably 0, 1 or 2; t occurs multiple times In the case of independently 0, 1, 2 or 3; u and v are independently 0, 1 or 2; w is 0 or 1; x is independently 0 or 1 to 12 identical or different ; Z is 0 or 1, wherein if the adjacent x or y is 0, z is 0; and wherein the benzene and naphthalene ring may additionally with one or more identical or different groups L instead.

In a preferred embodiment, the proportion of the monoreactive polymerizable liquid crystal precursor compound (preferably selected from the group consisting of Formulas II-1, II-13) in the liquid crystal material used in the method according to the present invention is preferably preferably It is in the range of 2% by weight to 20% by weight, more preferably in the range of 4% by weight to 12% by weight, and even more preferably in the range of 5% by weight to 10% by weight.

In another preferred embodiment, the proportion of the dual reactive polymerizable liquid crystal precursor compound (preferably selected from the group consisting of Formulas II-27) in the liquid crystal material used in the method according to the present invention is preferably preferably 0 weight. It is in the range of from 0 to 30% by weight, more preferably from 0% by weight to 20% by weight and even more preferably from 0% by weight to 10% by weight.

In another preferred embodiment, the proportion of the polyreactive polymerizable liquid crystal precursor compound in the liquid crystal material used in the method according to the present invention is preferably in the range of 0% by weight to 30% by weight, more preferably Preferably, it is in the range of 0% by weight to 20% by weight and even more preferably in the range of 0% by weight to 10% by weight.

The proportion of the palmitic polymerizable liquid crystal precursor compound (preferably selected from the formula CR8) in the preferred liquid crystal material for use in the method according to the invention is preferably in the range of from 1% by weight to 30% by weight. Internal, more preferably in the range of from 1% by weight to 20% by weight and even more preferably in the range of from 1% by weight to 10% by weight.

In another preferred embodiment, the polymerizable liquid crystal material comprises one or more non-polymerizable palmitic compounds, particularly those non-polymerizable palmitic compounds disclosed in WO 98/00428. Further, the non-polymerizable palmitic compound which is usually used is, for example, commercially available R/S-5011, R-811 or CB-15 (from Merck KGaA, Darmstadt, Germany).

The proportion of such palmitic non-polymerizable liquid crystal precursor compounds in preferred liquid crystal materials for use in the process according to the invention is preferably in the range of from 1% by weight to 20% by weight. More preferably, it is in the range of from 3% by weight to 15% by weight and even more preferably from 5% by weight to 10% by weight.

Preferably, the polymerizable liquid crystal material used in the method according to the present invention is a mixture of two or more (for example, 2 to 25) liquid crystal compounds.

The method according to the invention is not limited to a particular liquid crystal material, but can in principle be used for the alignment of all RMs known from the prior art. The RMs are preferably selected from the group consisting of rod-shaped or disc-shaped compounds exhibiting thermal or liquid-liquid liquid crystal properties, excellently rod-shaped compounds, or one or more types of liquid crystal intermediate phases in a certain temperature range. a mixture of such compounds. Such materials typically have excellent optical properties (e.g., reduced chromaticity) and can be simply and quickly aligned to the desired orientation, which is especially important for larger scale industrial production of polymeric films. The liquid crystal may be a small molecule (i.e., a monomer compound) or a liquid crystal oligomer.

In another preferred embodiment, a suitable polymerizable liquid crystal material according to the present invention comprises one or more polymerizable monoreactive, bireactive or polyreactive liquid crystal compounds preferably selected from the group consisting of compounds of formula II: P- Sp-MG-R ⁰ II

Wherein P is a polymerizable group, preferably a propenyl group, a methacryl group, a vinyl group, a vinyloxy group, a propenyl ether, an epoxy group, a propylene oxide or a styryl group; and Sp is a spacer or a single bond; MG is a rod-shaped liquid crystal original group, which is preferably selected from the formula M; M is -(A ²¹ -Z ²¹ ) _k -A ²² -(Z ²² -A ²³ ) _l -; A ²¹ to A ²³ appear every time Arbitrarily, independently of one another, an aryl, heteroaryl, heterocyclyl or alicyclic group substituted with one or more identical or different groups L, preferably one or more identical or different groups, as appropriate L-substituted 1,4-cyclohexylene or 1,4-phenylene, 1,4 pyridine, 1,4-pyrimidine, 2,5-thiophene, 2,6-dithieno[3,2-b: 2',3'-d]thiophene, 2,7-fluoro, 2,6-naphthalene, 2,7-phenanthrene; Z ²¹ and Z ²² are each independently -O-, -S-, - CO-, -COO-, -OCO-, -S-CO-, -CO-S-, -O-COO-, -CO-NR ⁰¹ -, -NR ⁰¹ -CO-, -NR ⁰¹ -CO-NR ⁰² , -NR ⁰¹ -CO-O-, -O-CO-NR ⁰¹ -, -OCH ₂ -, -CH ₂ O-, -SCH ₂ -, -CH ₂ S-, -CF ₂ O-, -OCF ₂ -, -CF ₂ S-, -SCF ₂ - _, -CH ₂ CH ₂ -, -(CH ₂ ) ₄ -, -CF ₂ CH ₂ -, -CH ₂ CF ₂ -, -CF ₂ CF ₂ -, -CH=N-, -N=CH-, -N=N-, -CH=CR ⁰¹ -, -CY ⁰¹ =CY ⁰² -, -C≡C-, -CH=CH-COO-, -OCO-CH=CH- or a single bond, preferably - COO-, -OCO-, -CO-O-, -O-CO-, -OCH ₂ -, -CH ₂ O-, -, -CH ₂ CH ₂ -, -(CH ₂ ) ₄ -, -CF ₂ CH ₂ -, -CH ₂ CF ₂ -, -CF ₂ CF ₂ -, -C≡C-, -CH=CH-COO-, -OCO-CH=CH- or a single bond; L has the formula I above One of the meanings defined in the formula; R ⁰ is H or, as the case may be, a fluorinated alkyl group having 1 to 20 C atoms, more preferably 1 to 15 C atoms, an alkoxy group, a sulfanyl group or an alkane a carbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group or an alkoxycarbonyloxy group, or Y ⁰ or P-Sp-; Y ⁰ is F, Cl, CN, NO ₂ , OCH ₃ , OCN, SCN, having 1 to 4 C atoms, optionally fluorinated alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy, or monofluorinated, oligofluorinated with 1 to 4 C atoms Or polyfluorinated alkyl or alkoxy group, preferably F, Cl, CN, NO ₂ , OCH ₃ or monofluorinated fluorinated or polyfluorinated alkyl having 1 to 4 C atoms or an alkoxy group; Y ⁰¹ and Y ⁰² are each and independently have the meaning as defined in the formula I; R ⁰¹ and R ⁰² are each Independently has the meaning as defined in the formula I; and k and l are each and independently 0 or 4, preferably 0, 1 or 2, most preferably 1.

Preferred polymerizable single reactivity, double is disclosed in, for example, WO 93/22397, EP 0 261 712, DE 195 04 224, WO 95/22586, WO 97/00600, US 5,518,652, US 5,750,051, US 5,770,107, and US 6,514,578. Reactive or polyreactive liquid crystal compound.

Other preferred polymerizable monoreactive, bireactive or polyreactive liquid crystal compounds are shown in the following list:

Wherein P ⁰ is a polymerizable group independently of each other, preferably a propenyl group, a methacryl group, a propylene oxide, an epoxy group, a vinyl group, a vinyloxy group, a propenyl ether or a benzene group. Vinyl; A ^0, in the case of multiple occurrences, independently of one another, 1,4-phenylene or trans-1,4-cyclohexylene, optionally substituted with 1, 2, 3 or 4 groups L; Z ⁰ independently of each other is -COO-, -OCO-, -CH ₂ CH ₂ -, -C≡C-, -CH=CH-, -CH=CH-COO-, -OCO -CH=CH- or a single bond; r is 0, 1, 2, 3 or 4, preferably 0, 1 or 2; t is 0, 1, 2 or 3 independently of each other in the case of multiple occurrences; u and v are independently 0, 1 or 2; w is 0 or 1; x and y are each independently 0 or 1 to 12 of the same or different integer; z is 0 or 1, wherein if x or y is adjacent If 0, then z is 0; further, wherein the benzene and naphthalene rings may be additionally substituted with one or more identical or different groups L.

The parameters R ⁰ , Y ⁰ , R ⁰¹ , R ⁰² and L have the same meanings as given in the above formula II.

The proportion of such monoreactive, direactive or polyreactive liquid crystal compounds in preferred liquid crystal materials for use in the process according to the invention is preferably in the range of from 30% by weight to 99% by weight, more preferably Preferably, it is in the range of 40% by weight to 95% by weight and even more preferably in the range of 50% by weight to 90% by weight.

The polymerizable liquid crystal material used in accordance with the present invention may also comprise one or more surfactants well known to the expert. The amount of the surfactant is preferably from 0% by weight to 3% by weight, more preferably from 0% by weight to 1.5% by weight, even more preferably from 0.1% by weight to 0.7% by weight, especially selected from commercially available interfacial activities. Agent TegoRad 2500 (Evonik) or FluorN 561 or 562 (Cytonix).

Suitable polymerizable liquid crystal materials for use in the process according to the invention may also comprise one or more dyes having a radiation wavelength adjusted to the absorption maximum for polymerization, especially UV dyes such as, for example, 4,4"-oxygen Azo alkyl ether or Tinuvin® dye (from Ciba AG).

The polymerizable liquid crystal material used in accordance with the present invention may also comprise one or more stabilizers or inhibitors selected, for example, from the commercially available Irganox® series (Ciba AG) (e.g., Irganox 1076) to prevent undesired spontaneous polymerization, in an amount comparable Preferably, it is from 0% to 0.1%, and preferably from 0% to 0.2%.

In a preferred embodiment, a suitable polymerizable liquid crystal material for use in the method according to the present invention comprises one or more monoreactive, polymerizable non-liquid crystalline pro-compounds, preferably in an amount of from 0% to 50%, preferably 0% to 20%. Typical examples are alkyl acrylates or alkyl methacrylates, preferably isobornyl methacrylate.

In another preferred embodiment, the polymerizable liquid crystal material used in accordance with the method of the present invention optionally comprises one or more dual or multiple reactions, in addition to or in addition to the dual reactive or polyreactive polymerizable liquid crystal precursor compound. The amount of the non-liquid crystalline raw compound is preferably from 0% to 50%, and preferably from 0% to 20%. Typical examples of the dual reactive monomer are alkyl diacrylate or alkyl dimethacrylate or hexanediol diacrylate having an alkyl group of 1 to 20 C atoms. A typical example of a polyreactive monomer is trimethylpropane trimethacrylate or pentaerythritol tetraacrylate.

It is also possible to add one or more chain transfer agents to the polymerizable liquid crystal material to modify the physical properties of the polymer film. Particularly preferred are thiol compounds, for example, monoreactive mercaptans (such as dodecanethiol) or polyreactive mercaptans (such as trimethylpropane tris(3-mercaptopropionate). Very preferred are liquids as disclosed, for example, in WO 96/12209, WO 96/25470 or US 6,420,001. Crystal or liquid crystal thiol. By using a chain transfer agent, the length of the free polymer chain in the polymer film and/or the length of the polymer chain between the two crosslinks can be controlled. As the amount of chain transfer agent increases, the length of the polymer chain in the polymer film decreases.

The polymerizable liquid crystal material according to the present invention may also comprise a polymeric binder or one or more monomers and/or one or more dispersing aids capable of forming a polymeric binder. Suitable adhesives and dispersing aids are disclosed, for example, in WO 96/02597. Preferably, however, the polymerizable material does not contain an adhesive or dispersing aid.

The polymerizable liquid crystal material may additionally comprise one or more additional components, such as a catalyst, a sensitizer, a stabilizer, an inhibitor, a chain transfer agent, a co-reacting monomer, a lubricant, a wetting agent, a dispersing agent, and a hydrophobic agent. Agents, adhesives, fluidity modifiers, defoamers, oxygen scavengers, diluents, reactive diluents, auxiliaries, colorants, dyes or pigments.

Preferably, the polymerizable liquid crystal material comprises: a) one or more non-pivoting monoreactive, bireactive or polyreactive polymerizable liquid crystal precursor compounds, b) one or more dichroic photoinitiators, c) one Or a plurality (polymerizable) of the palm compound, d) one or more surfactants as the case may be, e) one or more stabilizers as the case may be, f) one or more single reactivity, double depending on the situation Reactive or polyreactive polymerizable non-liquid crystalline precursor compound, g) optionally one or more non-polymerizable palmitic compounds, h) optionally presenting one or more of the absorption at a wavelength used to initiate photopolymerization The maximum dye, i) one or more chain transfer agents as appropriate, j) one or more stabilizers as appropriate.

More preferably, the polymerizable liquid crystal material comprises: a) one or more non-p-mono-reactive polymerizable liquid crystal precursor compounds, preferably in an amount of from 30% by weight to 95% by weight, very preferably from 50% by weight to 90% by weight, preferably selected from the group II- a compound of 1 and/or II-13; b) one or more non-pivotic double-reactive or polyreactive polymerizable liquid crystal precursor compounds, preferably in an amount of from 0.1% by weight to 30% by weight, preferably 0.5% % by weight to 20% by weight, preferably selected from the compounds of the formula II-6; c) one or more dichroic photoinitiators, preferably in an amount of from 3% by weight to 20% by weight, very preferably 5% by weight Up to 15% by weight, preferably selected from the group consisting of compounds of the formulae I-2a, I-3a and/or I-5a, more preferably selected from the compounds of the formulae I-2a or I-3a; d) one or more polymerisable Preferably, the palm compound, preferably one or more monoreactive palmitic compounds, is present in an amount of from 2% to 20% by weight, preferably from 5% to 10% by weight, preferably selected from the group consisting of a compound of CR8; e) one or more surfactants as appropriate; and f) one or more stabilizers as appropriate.

In a manner known per se (for example, by mixing one or more of the above-mentioned dichroic photoinitiators with one or more palmitic compounds, and one or more polymerizable liquid crystal compounds of formula II as defined above and The polymerizable liquid crystal material used in accordance with the present invention is prepared by mixing with other liquid crystal compounds and/or additives as appropriate. In general, the components of the desired amount to be used in smaller amounts are advantageously dissolved in the components constituting the main component at elevated temperatures. It is also possible to mix the solution of the components in an organic solvent (for example, acetone, chloroform or methanol) and remove the solvent again, for example, by distillation after thorough mixing.

The polymerizable liquid crystal material can be applied to the substrate by conventional coating techniques such as spin coating or knife coating. It can also be known by known printing techniques (for example, screen printing, lithography, roll-to-roll printing, printer printing, gravure printing, rotogravure printing, flexographic printing, embossing, embossing, heat). The polymerizable liquid crystal material is applied to the substrate by seal printing, ink jet printing or printing by means of a stamp or printing plate.

It is also possible to dissolve the polymerizable liquid crystal material in a suitable solvent. This solution is then coated or printed onto the substrate, for example by spin coating, printing or other known techniques, and the solvent is evaporated off prior to polymerization. In most cases, heating the mixture to promote solvent evaporation is suitable. For example, a standard organic solvent can be used as the solvent. The solvent may be selected, for example, from ethers (such as THF); ketones (such as acetone, methyl ethyl ketone, methyl propyl ketone or cyclohexanone); acetates (such as methyl acetate, acetic acid) Ethyl ester or butyl acetate or methyl acetoxyacetate); alcohols (such as methanol, ethanol or isopropanol); aromatic solvents (such as toluene or xylene); halogenated hydrocarbons (such as dichloromethane or Trichloromethane); glycols or esters thereof (such as PGMEA (propylene glycol monomethyl ether acetate), butyrolactone and the like). It is also possible to use a binary, ternary or ternary mixture of the above solvents.

For example, a glass or quartz plate or a plastic film or plate can be used as the substrate for the method according to the invention. For example, suitable and preferred plastic substrates are polyesters such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN), polyvinyl alcohol (PVA), polycarbonate (PC). Or a film of triethylenesulfonyl cellulose (TAC), which is excellently a PET or TAC film. For example, a uniaxially stretched plastic film can be used as the birefringent substrate. For example, PET films are commercially available from DuPont Teijin Films under the trade name Melinex®. In particular, the preferred substrate is TAC, PET, PVA, PE film or glass plate.

Preferably, the coated substrate according to the present invention is planar and is a structured substrate such as, for example, a Fresnel lens.

It is also possible to place a second substrate over the coated material before and/or during and/or after polymerization. The substrate may or may not be removed after polymerization. When two substrates are used, at least one of the substrates must be transmissive to actinic radiation for polymerization. An isotropic or birefringent substrate can be used. In the case where the substrate is not removed from the polymer film after polymerization, an isotropic substrate is preferably used.

In another preferred embodiment, the polymerizable liquid crystal material can also be filled into a prepared unit comprising a pair of opposing substrates. In a preferred embodiment, at least 1 μm to each other Preferably, the substrate is arranged at least at a distance of 2 μm and more preferably at least 3 μm from each other, wherein the layer of liquid crystal medium is positioned in the gap. Suitable filling methods are, for example, flow filling, capillary filling, and the like.

The substrate layers can be maintained at a defined spacing from each other by, for example, a spacer or a protruding structure in the layer. Typical spacer materials are well known to the expert, for example, spacers made of plastic, cerium oxide, epoxy, and the like.

The curing step according to the invention is preferably carried out by exposing the polymerisable liquid crystal material to linearly polarized actinic radiation when it is in its nematic or isotropic phase, preferably in its nematic phase.

Actinic radiation means the use of light, preferably with UV light or IR light. In the process according to the invention, the wavelength of the radiation should be chosen such that it causes dissociation of the dichroic photoinitiator and polymerization of the polymerizable compound. In this regard, the curing step is preferably performed by exposing the polymerizable liquid crystal material to linearly polarized UV radiation.

The wavelength of the radiation can be adjusted by a UV bandpass filter. The radiation wavelength is preferably in the range of from 250 nm to 450 nm, more preferably in the range of from 320 nm to 390 nm. Particularly preferably, the radiation wavelength is about 365 nm.

For example, a single UV lamp or a group of UV lamps can be used as a source of actinic radiation. When high lamp power is used, the curing time can be reduced. Another possible source of UV radiation is a laser.

By combining two or more point or linear source UV lamps such that the exposure is incident on the surface and the constructive or destructive interference of the light occurs, it is possible to position the lamp to obtain an intensity pattern commonly referred to as an interference pattern. The pattern can be reproduced/recorded in the obtained polymer film as a change in birefringence or optical axis, or as a planar or oblique patterning.

The linear polarization of actinic radiation can be achieved by methods known to the expert. Preferably, linear polarization is achieved by passing radiation through a suitable linear polarizer such as, for example, a commercially available wire grid polarizer (WGP).

The curing step according to the invention can be carried out under an inert gas atmosphere, preferably in a (heated) nitrogen atmosphere, however, curing in air is also possible.

As described above, the polymerizable liquid crystal material used in the present invention contains a dichroic photoinitiator. As with common photoinitiators, the dissociation of the dichroic photoinitiator and the formation of free radicals upon initiation of the appropriate wavelength will initiate polymerization of the monomer. The dichroic photoinitiator used in the polymerizable liquid crystal material of the present invention has the property that the light absorption depends on the molecular orientation of the molecule. Therefore, when the linearly polarized UV light is used for illumination, radicals which initiate polymerization are mainly produced, wherein the local guides are placed in parallel with the polarization direction. Local free radical generation results in a polymerizable liquid crystal material in an isotropic phase, a nematic phase, or a smectic phase, or a different local polymerization rate thereof to a palmitic variant. The polymerization rate of liquid crystal molecules oriented in parallel with the electric field of linearly polarized light is faster than the polymerization of liquid crystal molecules oriented perpendicular to the electric field of linearly polarized light. Thus, the difference in polymerization rates preferentially directs the director parallel to the linearly polarized UV light and ultimately induces birefringence into the polymer film due to complete polymerization and uniform alignment of the liquid crystal material in the polymer film.

The curing time depends, inter alia, on the reactivity of the polymerizable liquid crystal material, the thickness of the applied layer, the type of polymerization initiator, and the power of the UV lamp. The curing time is preferably 5 minutes, very good 3 minutes, best 1 minute. For mass production, A short cure time of 30 seconds is preferred.

Suitable UV radiation power is preferably in the range of 5 mW cm ^-2 to 200 mW cm ^-2 , more preferably in the range of 10 mW cm ^-2 to 175 mW cm ^-2 and most preferably in the range of 15 mW cm ^-2 to 150 mW cm ^-2 .

In combination with the applied UV radiation and over time, a suitable UV dose is preferably in the range of 25 mJ cm ^-2 to 7200 mJ cm ^-2 , more preferably in the range of 500 mJ cm ^-2 to 7200 mJ cm ^-2 and most preferably 3000 mJ cm ^-2 to 7200 mJcm ^-2 .

In a preferred embodiment, the curing step in accordance with the present invention is preferably performed by exposing different portions of the layer of polymerizable liquid crystal material to linearly polarized actinic radiation.

For example, this can be achieved by: - by masking techniques well known to the expert, for example by using a reticle, preferably a slit mask, or - By rotating the substrate continuously or stepwise, such as a rotary motion of a substrate having a layer of polymerizable liquid crystal material relative to a radiation source or an incident radiation beam (see Figures 1 and 6) or horizontal motion (see Figure 8).

The principles of the method of the present invention can be illustrated using examples. In the meantime, this example also shows a first preferred embodiment of the method according to the invention without limiting the scope of the invention to this particular example.

Preferably, the liquid crystal molecules in the polymer film are aligned in a planar orientation with respect to the major plane of the substrate. This planar orientation of the liquid crystal molecules in the resulting polymer film can be achieved when the source of radiation in the curing step is positioned at an angle normal to the major plane of the substrate.

A typical configuration of a production method according to the present invention is depicted in FIG. 1, and the configuration includes:

a light source (1) positioned perpendicular to the main plane of the substrate,

- a component for collimating the beam, as the case may be,

- Rotatable linear polarizer (2),

- a rotatable reticle (3),

a substrate (4) having a layer of polymerizable liquid crystal medium, and

a heating source (5) adjacent to the substrate, which is arranged on the rotatable table (6).

- in a preferred embodiment, the substrate (4) having a layer of polymerizable liquid crystal medium and the heating source (5) adjacent to the substrate are rotated horizontally or continuously around an axis perpendicular to the main plane, simultaneously Both the linear polarizer and the reticle are fixed in their orientation. Thus, linearly polarized light will be used to illuminate only portions of the layer of polymerizable liquid crystal medium that are not masked, while the direction of the electric field vector of the linearly polarized light remains constant throughout the curing step.

- In another preferred embodiment, both the reticle (3) and the linear polarizer (2) are rotated horizontally or continuously about an axis perpendicular to their principal plane, while the linear polarizer is fixed with polymerizable liquid crystal Orientation of the substrate of the layer of material orientation. Therefore, linear polarization will be used The light illuminates only a portion of the layer of the polymerizable liquid crystal medium while changing the direction of the electric field vector of the linearly polarized light throughout the curing step.

By adjusting the orientation of the wire grid polarizer relative to the slit mask (see Figures 2 and 4), a radially aligned polymer film (Figure 3) or concentrically aligned polymer can be obtained from the above method according to the invention. Membrane (Figure 5).

Another example may be used to illustrate the principles of the method of the present invention. In the meantime, this example also shows a second preferred embodiment of the method according to the invention without limiting the scope of the invention to this particular example.

Another exemplary configuration of a production method according to the present invention is depicted in FIG. 6, and the configuration includes:

a light source (7) positioned at an oblique angle (>0° < 90°) with respect to the main plane of the substrate,

- a member for collimating the beam (8) as the case may be,

a linear polarizer (9) and a reticle (10) positioned at the same oblique angle (>0° < 90°) in front of the light source,

a substrate (11) having a layer of polymerizable liquid crystal medium, and

a heating source (12) adjacent to the substrate, which is arranged on the rotatable table (13).

- in a preferred embodiment, the substrate (11) having a layer of polymerizable liquid crystal medium and the heating source (12) adjacent to the substrate are continuously rotated horizontally about an axis perpendicular to the main plane, while linearly polarizing Both the device and the light source are fixed in their orientation.

- In another preferred embodiment, both the linear polarizer and the light source are rotated on a circular path above the substrate (11) having a layer of polymerizable liquid crystal medium.

After one of the above processes, it is possible to produce a polymer film in which the liquid crystal material is generally aligned with respect to the main plane of the substrate in a slanted radial orientation (> 0° < 90°) (Fig. 7).

Preferably, the radiation angle is between more than 0° and less than 90°, more preferably between more than 10° and less than 80°, or even more preferably between more than 20° and less than 70°, It is in particular between more than 30° and less than 60° and in particular approximately 45°.

The invention also relates to polymeric films obtainable or obtained by the methods described above and below.

However, it is also excellent that the oriented polymer film of the present invention is used as, for example, a retardation film or a compensation film in an LCD to improve contrast and brightness at a large viewing angle and to reduce chromaticity. The polymer films can be used outside of the switchable liquid crystal cell in the LCD or between a switchable liquid crystal cell and a substrate (typically a glass substrate) containing a switchable liquid crystal medium (in-line application).

Various types of optical retarders are known. For example, an "A film" (or A plate) is an optical retarder that utilizes a layer of uniaxial birefringent material with an anomalous axis oriented parallel to the plane of the layer. In this regard, a "C film" (or C plate) is an optical retarder utilizing a layer of uniaxial birefringent material having an anomalous axis oriented perpendicular to the plane of the layer. However, the patterning or tilting variants of the retarders described above are also in accordance with the invention.

According to the illumination angle described above, the polymer film obtainable or obtained by the method according to the invention can be used as a patterned A when positioning the radiation source in the curing step at an angle perpendicular to the main plane of the substrate. The plate (at least two different plane orientations of the directors of the liquid crystal molecules of the polymer film) or as a patterned O plate when the radiation source is positioned at an oblique angle (>0° < 90°) relative to the main plane of the substrate (at least two different oblique orientations of the directors of the liquid crystal molecules in the polymer film).

In another preferred embodiment, the polymer film obtainable or obtained by the method according to the invention can also be used as a flat surface lens, exhibiting a director orientation of a concave or convex type, or as a gradient index. A lens (GRIN), both the flat surface lens and the gradient index lens can be used for an autostereoscopic display device.

The optical retardation (δ(λ)) of the polymer film as a function of the wavelength of the incident beam (λ) is given by the following equation (6): δ(λ)=(2πΔn.d)/λ (6)

Where (Δn) is the birefringence of the film, (d) is the thickness of the film and λ is the wavelength of the incident beam.

According to Snellius' law, the birefringence that varies with the direction of the incident beam is defined as Δn = sin Θ / sin Ψ (7)

Wherein sin Θ is the incident angle or tilt angle of the optical axis in the film and sin Ψ is the corresponding reflection angle.

Based on these laws, the birefringence and the thickness of the corresponding optically retarded film and the tilt angle of the optical axis in the film (see Berek compensator). Thus, skilled artisans have perceived that different optical retardations or different birefringences can be induced by adjusting the orientation of the liquid crystal molecules in the polymer film.

The birefringence (?n) of the polymer film according to the present invention is preferably in the range of 0.01 to 0.30, more preferably in the range of 0.01 to 0.25, and even more preferably in the range of 0.01 to 0.16.

The thickness of the polymer film obtained by the method according to the invention is preferably in the range of from 3 μm to 30 μm, more preferably in the range of from 3 μm to 20 μm and even more preferably in the range of from 3 μm to 10 μm.

In a preferred embodiment, the thickness of the polymeric film is such that a phase transition of π/2 is introduced, which is then circularly polarized. Since π/2 is equal to a quarter wave, this retarder is called a quarter wave plate. A quarter-wave plate as explained previously will change the linear polarization to circular polarization and vice versa.

In an equally preferred embodiment, the thickness of the polymeric film is such that a phase change of π is introduced which corresponds to a half wave plate. The half-wave plate keeps the linear polarization linear, however, the half-wave plate will rotate at an angle of 2θ; where θ is the angle between the incident polarization direction and the fast axis of the material.

In another preferred embodiment, the thickness of the polymeric film is such that the change in the retardation of one wave (2π) is equal to the retardation and no change in the incident beam.

The polymeric film of the present invention can also be used as an alignment film for other liquid crystal or RM materials as described, for example, in WO 2006/039980 A1. For example, the polymeric films can be used in an LCD to induce or modify the alignment or alignment of the switchable liquid crystal medium thereon. Subsequent layers of polymerizable liquid crystal material. In this way, a stack of polymerized liquid crystal films can be prepared.

The polymer film of the present invention can be used in various liquid crystal displays, for example, displays having vertical alignment, such as alignment phase deformation (DAP), electronically controlled birefringence (ECB), and color super vertical (CSH). Vertical alignment type (VA), vertical alignment nematic or vertical alignment cholesteric (VAN or VAC), multi-domain vertical alignment (MVA), or patterned vertical alignment (PVA) mode; Curved or hybrid aligned displays, such as optically compensated bend units or optically compensated birefringence (OCB), reflective OCB type (R-OCB), hybrid aligned nematic (HAN) or pi-unit (π-unit Type) display with torsional alignment, such as twisted nematic (TN), highly twisted nematic (HTN), super twisted nematic (STN), active matrix driven TN (AMD-TN) Mode; an in-plane switching (IPS) mode display; or a display that switches in an optically isotropic phase.

The invention has been described above and below with particular reference to the preferred embodiments. It should be understood that various changes and modifications may be made herein without departing from the spirit and scope of the invention.

Many of the compounds mentioned above and below or mixtures thereof are commercially available. As described in the literature (for example in standard works such as Houben-Weyl, Methoden der Organischen Chemie [Methods of Organic Chemistry], Georg-Thieme-Verlag, Stuttgart), all such compounds are known or may be by themselves Known methods are, in particular, prepared under the reaction conditions known and suitable for the reactions. Variants of methods known per se but not mentioned herein may also be utilized herein. The plural forms of the terms herein are to be construed as including the singular, and vice versa, unless the context clearly indicates otherwise.

Throughout this application, all concentrations are given in weight percent unless otherwise specifically stated, and with respect to the individual complete mixtures, all temperatures are given in degrees Celsius, and all temperature differences are given in degrees Celsius. All physical properties unless otherwise stated They have been determined according to or according to "Merck Liquid Crystals, Physical Properties of Liquid Crystals" of the state of November 1997 of Merck KGaA, Germany, and are given for a temperature of 20 °C. Optical anisotropy (Δn) was determined at a wavelength of 589.3 nm.

In the context of the description and the scope of the claims, the words "comprise" and "including" and variations of such terms (eg, including and including) mean "including" (but not limited to) and do not (and do not) exclude other components. On the other hand, the word "comprising" also encompasses the term "consisting of" but is not limited to the term.

In the context of the description and the scope of the patent application, the words "available" and "acquired" and variations of such terms mean "including (but not limited to)" and do not (and not exclude) Other components. On the other hand, the word "available" also covers the term "acquired" but is not limited to the term.

It will be appreciated that variations may be made to the above-described embodiments of the invention, but such variations are still within the scope of the invention. Alternative features for the same, equivalent or similar purpose may be substituted for each feature disclosed in this specification unless otherwise stated. Therefore, unless expressly stated otherwise, each feature disclosed is only one example of a series of common equivalent or similar features.

All of the features disclosed in this specification can be combined in any combination, except that at least some combinations of such features and/or steps are mutually exclusive. In particular, the preferred features of the invention are applicable to all aspects of the invention and may be used in any combination. Also, features described in a non-essential combination may be used separately (not in combination).

It will be appreciated that many of the above features, particularly preferred embodiments, are inherently inventive and are not intended to be a part of an embodiment of the invention. In addition to or in lieu of any invention currently claimed, independent protection may be sought for such features.

The invention will be described in more detail with reference to the following examples, which are intended to be illustrative and not restrictive.

Instance

1. Example of mixture

1.1 Mixture M1

Preparation of the following polymerizable liquid crystal materials

Clarification point: 40.0 ° C

1.2. Mixture M2

Preparation of the following polymerizable liquid crystal materials

Compound amount (% w/w)

Clarification point 48.7 ° C

1.3. Mixture M3

Preparation of the following polymerizable liquid crystal materials

Clarification point: 43.5 ° C

2. Unit production

5 μm spacer beads were mixed with Norland 81 UV gel. The unit is generated by placing a droplet of the glue/bead mixture on the corner of the blank glass slide, providing a second blank glass slide at the top, and subsequently curing with UV light for 60 seconds (25 mW) .

3. Radial alignment

The mixture M3 was flow-filled to a unit on a hot plate at 80 °C. The temperature was then adjusted to 60 ° C in 60 seconds. Place the unit on the electric rotating platform and set the speed to 3° per second. For radial alignment, the WGP is set to be parallel with respect to the slit of the slit mask (Fig. 2). The unit was then exposed to 25 mW of polarized UV light (365 nm bandpass filter) at 60 ° C for 60 seconds. Mixture M3 provides a clear transparent polymer film with good radial orientation (see Figure 3).

In the same manner, a clear transparent polymer film having a good radial orientation can be prepared from the mixtures M1 and M2.

3.1 Radial alignment

The mixture M3 was spin coated on the blank glass at 1000 rpm for 30 seconds. The film was placed on a hot plate at 56 ° C for 60 seconds. The film was then placed in a nitrogen chamber at 34 ° C for 60 seconds while purging the chamber with nitrogen. Place the chamber on the electric rotating platform and set the speed to 3° per second. For radial alignment, the WGP is set to be parallel with respect to the slit of the slit mask (Fig. 2). The unit was then exposed to 120 mW of polarized UV light (365 nm bandpass filter) under nitrogen at 34 °C for 40 seconds. Mixture M3 provides a clear, transparent polymer film with good radial orientation (see Figure 3).

4. Concentric alignment

The mixture M3 was flow-filled to a unit on a hot plate at 80 °C. This temperature was then adjusted to 60 ° C in 60 seconds. Place the unit on the electric rotating platform and set the speed to 3° per second. For radial alignment, the WGP is set to be perpendicular to the slit of the slit mask (Fig. 4). The unit was then exposed to 25 mW of polarized UV light (365 nm bandpass filter) at 60 ° C for 60 seconds. Mixture M3 provides a clear, transparent polymer film with good concentric orientation (see Figure 5).

In the same manner, a clear transparent polymer film having a good concentric orientation can be prepared from the mixtures M1 and M2.

5. Tilt radial alignment

The mixture M3 was flow-filled to a unit on a hot plate at 80 °C. This temperature was then adjusted to 60 ° C in 60 seconds. Place the unit on the electric rotating platform and set the speed to 3° per second. The UV lamp is set at an oblique angle of 45° with respect to the main plane of the unit. The WGP is set to be parallel with respect to the slit of the slit mask (Fig. 2). The unit was then exposed to 25 mW of polarized UV light (365 nm bandpass filter) at 60 ° C for 60 seconds. Mixture M3 provides a clear, transparent polymer film with a good orientation in a convexly oriented form (see Figure 7).

In the same manner, a clear, transparent and flat lens film having a good orientation in a convexly oriented form can be prepared from the mixtures M1 and M2.

Claims (20)

A method of preparing a patterned polymer film, the method comprising the steps of: a) providing a layer of a polymerizable liquid crystal material to a substrate, the polymerizable liquid crystal material comprising at least one dichroic photoinitiator and at least one pair of palms a compound; b) adjusting the temperature of the polymerizable liquid crystal material to a temperature at which the polymerizable liquid crystal material is in its nematic or isotropic phase; and c) irradiating the polymerizable liquid crystal material by using linearly polarized actinic radiation The polymerization and orientation are performed, and the angle between the layer of the polymerizable liquid crystal material and the direction of the electric field vector of the linearly polarized actinic radiation is varied to form the polymerizable liquid crystal material into a polymer film. The method of claim 1, wherein in step c), the liquid crystal material is illuminated while the liquid crystal material is in the nematic phase. The method of claim 1, wherein the step c) is performed while continuously or stepwise rotating the substrate having the layer of the polymerizable liquid crystal material. The method of claim 1, wherein the step c) is performed by continuously or stepwise rotating a mask or a linear polarizer or both, and each of the mask and the linear polarizer is located on the substrate and a light source between. The method of any one of claims 1 to 4, wherein the polymerizable liquid crystal material comprises at least one monoreactive, bireactive or polyreactive polymerizable liquid crystal precursor compound, at least one pair of palm compound, and at least one dichroic Color photoinitiator. The method of any one of claims 1 to 4, wherein the polymerizable liquid crystal material comprises at least one monoreactive polymerizable liquid crystal precursor compound, at least one double reactive or polyreactive polymerizable liquid crystal precursor compound, at least one pair of palms a compound and at least one dichroic photoinitiator. The method of any one of claims 1 to 4, wherein the polymerizable liquid crystal material comprises There is less than one monoreactive pair of palmitic polymerizable liquid crystal precursor compounds, at least one monoreactive, double reactive or polyreactive non-pivotic polymerizable liquid crystal precursor compound and at least one dichroic photoinitiator. The method of any one of claims 1 to 4, wherein the polymerizable liquid crystal material comprises at least one double reactive or polyreactive pair of palmitic polymerizable liquid crystal precursor compounds, at least one single reactive, double reactive or multiple reactive A non-pivoted polymerizable liquid crystal precursor compound and at least one dichroic photoinitiator. The method of any one of claims 1 to 4, wherein the polymerizable liquid crystal material comprises at least one non-polymerizable palmitic compound, at least one monoreactive, double reactive or multireactive non-pivotic polymerizable liquid crystal The original compound and at least one dichroic photoinitiator. The method of any one of claims 1 to 4, wherein the dichroic photoinitiator is selected from the group consisting of a compound of formula I, Wherein A ^{11 is} independently, independently of one another, an aryl, heteroaryl, aliphatic or heterocyclic group which is unsubstituted or substituted with one or more identical or different groups L; Z ^{11 is} in each In the second occurrence, they are -O-, -S-, -CO-, -COO-, -OCO-, -S-CO-, -CO-S-, -O-COO-, -CO-NR ⁰¹ independently of each other. -, -NR ⁰¹ -CO-, -NR ⁰¹ -CO-NR ⁰² , -NR ⁰¹ -CO-O-, -O-CO-NR ⁰¹ -, -OCH ₂ -, -CH ₂ O-, -SCH ₂ -, -CH ₂ S-, -CF ₂ O-, -OCF ₂ -, -CF ₂ S-, -SCF ₂ -, -CH ₂ CH ₂ -, -(CH ₂ ) ₄ -, -CF ₂ CH ₂ -, -CH ₂ CF ₂ -, -CF ₂ CF ₂ -, -CH=N-, -N=CH-, -N=N-, -CH=CR ⁰¹ -, -CY ⁰¹ =CY ⁰² -,- C≡C-, -CH=CH-COO-, - OCO-CH=CH- or a single bond; m is 0, 1, 2 or 3; r is 0, 1, 2, 3 or 4; In the case of a second occurrence, H, F, Cl, CN or an unalkylated or halogenated alkyl group having 1 to 5 C atoms, an alkoxy group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkyl group A carbonyloxy or alkoxycarbonyloxy group; R ¹¹ is H, halogen, CN, NO ₂ , NCS, SF ₅ , P-Sp-; or unsubstituted or monosubstituted by F, Cl, Br, I or CN Or more substituted with 1 to 20 a linear or branched alkyl group of one C atom, and wherein one or more non-adjacent CH ₂ groups are independently of each other in each case in such a manner that O and/or S atoms are not directly bonded to each other Substitution or via -O-, -S-, -NR ⁰¹ -, -SiR ⁰¹ R ⁰² -, -CO-, -COO-, -OCO-, -OCO-O-, -NR ⁰¹ -CO-, -CO -NR ⁰¹ -, -NR ⁰¹ -CO-NR ⁰² -, -S-CO-, -CO-S-, -CY ⁰¹ =CY ⁰² - or -C≡C-substitution; or R ¹⁴ ;P is one a polymeric group; Sp is a spacer group or a single bond; R ^{12-13 is} independently H or unsubstituted or monosubstituted or polysubstituted by F, Cl, Br, I or CN has 1 to 20 a linear or branched alkyl group of a C atom, and wherein one or more non-adjacent CH ₂ groups are independently unsubstituted in each case in such a manner that O and/or S atoms are not directly bonded to each other Or via -O-, -S-, -NR ⁰¹ -, -SiR ⁰¹ R ⁰² -, -CO-, -COO-, -OCO-, -OCO-O-, -NR ⁰¹ -CO-, -CO- NR ⁰¹ -, -NR ⁰¹ -CO-NR ⁰² -, -S-CO-, -CO-S-, -CY ⁰¹ =CY ⁰² - or -C≡C-substitution; R ¹⁴ represents -OH, -NR ⁰¹ R ⁰² or Y ⁰¹ and Y ⁰² each independently represent H, halogen or CN; and R ⁰¹ and R ⁰² are each independently H or a linear or branched alkyl group having 1 to 5 C atoms. The method of any one of claims 1 to 4, wherein the proportion of the dichroic photoinitiator in the liquid crystal material is generally in the range of from 1% by weight to 25% by weight. The method of any one of claims 1 to 4, wherein the pair of palm compounds have Spiral torsion (HTP) of 25 μm ^-1 . The method of any one of claims 1 to 4, wherein the proportion of the pair of palm compounds in the liquid crystal material is generally in the range of 2% by weight to 20% by weight. The method of any one of claims 1 to 4, wherein step c) is performed by exposing the polymerizable liquid crystal material to linearly polarized UV radiation. The method of any one of claims 1 to 4, wherein the polymerizable liquid crystal material has a planar orientation with respect to a principal plane of the substrate after the illuminating step c). The method of any one of claims 1 to 4, wherein the polymerizable liquid crystal material has an oblique orientation (>0° < 90°) with respect to one of the principal planes of the substrate after the illuminating step c). The method of any one of claims 1 to 4, wherein the illuminating in step c) is performed at an oblique angle (>0° < 90°) with respect to one of the principal planes of the substrate. A polymer film obtainable by the production method according to any one of claims 1 to 17. A use of a polymer film of claim 18 or a polymer film obtained by the method of any one of claims 1 to 17 for use in decorative or security applications, liquid crystal displays for window applications (LCD) Or as an alignment layer or an optical retardation film in other optical or electro-optical devices. An optical or electro-optic device comprising at least one polymer film of claim 18 or a polymer film obtained by the method of any one of claims 1 to 17.